Synthesis and Cation-Binding Properties of (1→6)-2,5-Anhydro-D-glucitol with 3,4-Di-O-Pentyl and Decyl Groups by Cyclopolymerization of 1,2:5,6-Dianhydro-D-mannitols

Abstract

The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF₃OEt₂ and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF₃O-decyl₂ comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl₃, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity in the order Cs⁺ > Rb⁺ > K⁺ ? Na⁺ > Li⁺. The ratio of K⁺ and Na⁺, K⁺/Na⁺, was 4.6 for 2a, 5.1 for 2b, and 7.1 for 2c in the increasing order 2a < 2b > 2c.     

Nano-crater formation on a Si(1 1 1)-(7 × 7) surface by slow highly charged ion-impact

Using scanning tunneling microscopy (STM) and time of flight secondary ion mass spectrometry (TOF/SIMS), we observed radiation effects on a Si(1 1 1)-(7 × 7) surface in the collision of a single highly charged ion (HCI) with a charge state q up to q = 50. The STM observation with atomic resolution revealed that a nanometer sized crater-like structure was created by a single HCI impact, where the size increased rapidly with q. The secondary ion yields also increased with q in which multiply charged Si ions (Siⁿ⁺) were clearly observed in higher q HCI-collisions. The sputtering mechanism is briefly discussed, based on the so-called Coulomb explosion model.     

Exiguolide, a new macrolide from the marine sponge Geodia exigua

A new 20-membered macrolide designated exiguolide has been isolated from the marine sponge Geodia exigua, and its structure determined by interpretation of spectroscopic data. Exiguolide specifically inhibited fertilization of sea urchin (Hemicentrotus pulcherrimus) gametes but not embryogenesis of the fertilized egg.     

Towards single cell heat shock response by accurate control on thermal confinement with an on-chip microwire electrode

Metal electrodes with micron scale width enable the heating of less than a dozen cells in a confluent layer at predictable temperatures up to 85 °C with an accuracy of ±2 °C. Those performances were obtained by a preliminary robust temperature calibration based on biotin-rhodamine fluorescence and by controlling the temperature map on the substrate through thermal modeling. The temperature accuracy was proved by inducing the expression of heat shock proteins (HSP) in a few NIH-3T3 cells through a confined and precise temperature rise. Our device is therefore effective to locally induce a heat shock response with almost single-cell resolution. Furthermore, we show that cells heated at a higher temperature than the one of heat shock remain alive without producing HSP. Electrode deposition being one of the most common engineering processes, the fabrication of electrode arrays with a simple control circuit is clearly within reach for parallel testing. This should enable the study of several key mechanisms such as cell heat shock, death or signaling. In nanomedicine, controlled drug release by external stimuli such as for example temperature has attracted much attention. Our device could allow fast and efficient testing of thermoactivable drug delivery systems.     

Rational Design and Identification of a Non‐Peptidic Aggregation Inhibitor of Amyloid‐β Based on a Pharmacophore Motif Obtained from cyclo[‐Lys‐Leu‐Val‐Phe‐Phe‐]

Inhibition of pathogenic protein aggregation may be an important and straightforward therapeutic strategy for curing amyloid diseases. Small‐molecule aggregation inhibitors of Alzheimer’s amyloid‐β (Aβ) are extremely scarce, however, and are mainly restricted to dye‐ and polyphenol‐type compounds that lack drug‐likeness. Based on the structure‐activity relationship of cyclic Aβ16–20 (cyclo‐[KLVFF]), we identified unique pharmacophore motifs comprising side‐chains of Leu², Val³, Phe⁴, and Phe⁵ residues without involvement of the backbone amide bonds to inhibit Aβ aggregation. This finding allowed us to design non‐peptidic, small‐molecule aggregation inhibitors that possess potent activity. These molecules are the first successful non‐peptidic, small‐molecule aggregation inhibitors of amyloids based on rational molecular design.     

Qβ measurements of 158, 159Pm , 159, 161Sm , 160-165Eu , 163Gd and 166Tb using a total absorption BGO detector

Q _β values of the neutron-rich isotopes of ^160-165Eu and ¹⁶³Gd were measured for the first time using a total absorption bismuth germanate (BGO) detector, and previously obtained data on ^{158, 159}Pm , ^{159, 161}Sm and ¹⁶⁶Tb were re-analyzed. These radioactive sources were prepared by an on-line mass separator (Tokai-ISOL) following the ²³⁸U (p,f reaction. The deduced Q _β values are the following: 6085(80)keV for ¹⁵⁸Pm , 3805(65)keV for ¹⁵⁹Sm , 5460(140)keV for ¹⁵⁹Pm , 4705(60)keV for ¹⁶⁰Eu , 5065(130)keV for ¹⁶¹Sm , 3705(60)keV for ¹⁶¹Eu , 5575(60)keV for ¹⁶²Eu , 4690(70)keV for ¹⁶³Eu , 3170(70)keV for ¹⁶³Gd , 6430(70)keV for ¹⁶⁴Eu , 5800(120)keV for ¹⁶⁵Eu , and 4695(70)keV for ¹⁶⁶Tb . Moreover, the deduced mass excesses and two-neutron separation energies ( S _2n values) were compared with those of the atomic mass evaluations and theoretical predictions.     

A hybrid density-functional study of the one-dimensional ferromagnetic ordering of (BDTA)[Ni(mnt)2]

The one-dimensional intermolecular ferromagnetic interaction of a charge-transfer (CT) complex, (BDTA)[Ni(mnt)₂] (BDTA: 1,3,2-benzodithiazolyl, mnt: maleonitriledithiolate), is studied by the Kohn–Sham hybrid density functional method, in order to understand the mechanism of the magnetism. All possible effective exchange integrals, J, between the spin pairs of the system indicate that a ferromagnetic interaction (J = 172 cm⁻¹) exists along the b-axis. Magnetic susceptibility, simulated with the ab initio determined J values by the quantum Monte Carlo (QMC) method, is qualitatively consistent with that measured experimentally.     

Sparsely substituted chlorins as core constructs in chlorophyll analogue chemistry. II. Derivatization

Stable chlorins bearing few or no substituents have been subjected to a variety of reactions including demetalation, magnesium insertion, oxochlorin formation, and bromination followed by Suzuki coupling. The kinetics of deuteration also have been determined for two oxochlorins and a series of chlorins bearing 0, 1, 2, or 3 meso-aryl substituents.     

A study of hepato-biliary and alimentary scintigrams using a triple tracer method

In order to evaluate the gastric emptying and postprandial mixing of bile with food, the scintigraphies of hepatobiliary and gastrointestinal tracts by using three different kinds of radioisotopes were performed simultaneously (99mTc-E.HIDA for hepatobiliary scintigraphy, 111In-DTPA containing orange juice and 131I-albumin containing scrambled egg for gastrointestinal scintigraphy). This method was available for observation of gastric emptying of liquid and solid foods and also examination of the mixing effect of bile and food quantitatively.     

Asymptotic expansions of the distributions of some test statistics for Gaussian ARMA processes

Let {X_t} be a Gaussian ARMA process with spectral density f_θ(λ), where θ is an unknown parameter. The problem considered is that of testing a simple hypothesis H:θ = θ₀ against the alternative A:θ ≠ θ₀. For this problem we propose a class of tests , which contains the likelihood ratio (LR), Wald (W), modified Wald (MW) and Rao (R) tests as special cases. Then we derive the χ² type asymptotic expansion of the distribution of T up to order n⁻¹, where n is the sample size. Also we derive the χ² type asymptotic expansion of the distribution of T under the sequence of alternatives A_n: θ = θ₀ + /√n, ε > 0. Then we compare the local powers of the LR, W, MW, and R tests on the basis of their asymptotic expansions.